Quaternary ammonium compounds as bleach activators and their preparation

ABSTRACT

Quaternary ammonium compounds, their preparation and use Compounds of the formula I ##STR1## are claimed, as are their preparation and use, in which the radicals R 1 , R 2  and R 3  are organic substituents, L is either a lactam or a cyclic amidine and X is an appropriate anion. The novel compounds are employed as bleach activators in cleaners and detergents which have a bleaching action.

This is a divisional of application Ser. No. 08/881,661 filed on Jun.24, 1997, now U.S. Pat. No. 5,877,325.

This invention relates to quaternary ammonium compounds, to theirpreparation and to detergent compositions which include these quaternaryammonium compounds as bleach activators.

It is known that the bleaching power of peroxide bleaches such asperborates, percarbonates, persilicates and perphosphates can beimproved so that bleaching begins at lower temperatures, for instance ator below 60° C., by adding the precursors of bleaching peroxy acids,which are often referred to as bleach activators.

Numerous substances are known in the prior art as bleach activators.They are usually reactive organic compounds with an O-acyl or N-acylgroup, which combine in alkaline solution with a source of hydrogenperoxide to form the corresponding peroxy acids.

Representative examples of bleach activators are for instanceN,N,N',N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA),xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS),sodium trimethylhexanoyloxybenzenesulfonate (STHOBS),tetraacetylglycoluril (TAGU), tetraacetylcyanic acid (TACA),di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).Reference may be made, for example, to GB-A-836 988, GB-A-907 356,EP-A-0 098 129 and EP-A-0 120 591.

Over time, cationic peroxy acid precursors containing for example, inaddition to O-acyl or N-acyl groups, a quaternary ammonium group havegained in importance because they are highly effective bleachactivators. Cationic peroxy acid precursors of this kind are described,for example, in U.S. Pat. No. 5,460,747, U.S. Pat. No. 5,047,577, U.S.Pat. No. 4,933,103, U.S. Pat. No. 4,751,015, U.S. Pat. No. 4,397,757,GB-1 382 594, WO-95 21150, EP-A-403 152, EP-A-427 224, EP-A-402 971,EP-371 809 and EP-A-284 292. Corresponding free, stable quaternaryperacids are described, for example, in EP-A-340 754 and WO-94 01399.

It has surprisingly now been found that certain quaternary bleachactivators as described below have a better bleaching action than theprior art bleach activators. In addition, the novel bleach activatorscan be prepared with fewer synthesis steps, and therefore in a moreecologically and economically favorable manner, than the prior artbleach activators.

The invention provides compounds of the formula I ##STR2## in which a)R₁, R₂ and R₃ independently of one another are C₁ - to C₂₄ -alkyl, aryl,C₂ -C₂₄ -alkenyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, or CH₂ --CO--L, or

b) R₂ and R₃, together with the nitrogen atom to which they areattached, form a ring having from 4 to 6 carbon atoms, which ring may inaddition to the nitrogen atom contain, in place of carbon atoms, one ortwo oxygen atoms or a group ##STR3## L is a group of the formula##STR4## n is a number from 3 to 5, m is a number from 2 to 4

and X is an anion.

Preferred anions are chloride, bromide, iodide, fluoride, sulfate,hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- anddihydrogen phosphate, pyrophosphate, metaphosphate, nitrate,methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, phosphonate,methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonateand p-toluenesulfonate.

The substituents R₁, R₂ and R₃ independently of one another arepreferably unsubstituted C₁ -C₄ -alkyl, unsubstituted C₂ -C₄ -alkenyl orphenyl. L is preferably a pyrrolidone group.

Particular preference is given to short-chain(trialkylammonium)acetylpyrrolidone chlorides and corresponding(trialkylammonium)acetyl-imidazole chlorides with C₁ - to C₄ -alkylgroups, especially 2-(N,N,N-trimethylammonium)acetylpyrrolidonechloride, 2-(N,N,N-triethylammonium)acetylpyrrolidone chloride,2-(N,N-diethyl-N-methylammonium)acetylpyrrolidone chloride, and thecorresponding imidazole derivatives.

The invention additionally provides a process for preparing thesecompounds. The general examples below will be used to illustrate thesynthesis pathways leading to the novel cationic bleach activators.

GENERAL EXAMPLE 1

A lactam and an appropriate auxiliary base are charged in an organicsolvent to a reactor. Chloroacetyl chloride is added dropwise, withcooling, at temperatures between 0 and 30° C., preferably at 5° C. Aftera reaction period of from 3 to 12 hours at temperatures between 10 and30° C., preferably at 25° C., the resulting precipitate is filtered off.The subsequent reaction can proceed without isolation of the resultingN-(chloroacetyl)amide beforehand. Following the addition of a tertiaryamine, reaction is carried out at temperatures of between 20 and 100°C., preferably between 70 and 80° C., to give the corresponding2-(N,N,N-trialkylammonium)acetyllactam chloride. In the case of theshort-chain amines preferably employed, the reaction is carried out inan autoclave if desired.

GENERAL EXAMPLE 2

A lactam and an appropriate auxiliary base are charged in an organicsolvent to a reactor. Chloroacetyl chloride is added dropwise, withcooling, at temperatures between 0 and 30° C., preferably at 5° C. Aftera reaction period of from 3 to 12 hours at temperatures between 10 and30° C., preferably at 25° C., the resulting precipitate is filtered off.The subsequent reaction can proceed without isolation of the resultingN-(chloroacetyl)amide beforehand. At temperatures between 0 and 50° C.,preferably with cooling at 20° C., a secondary amine is added. Followinga reaction period of from 3 to 12 hours at temperatures of between 10and 50° C., preferably at 25° C., the resulting precipitate is filteredoff. With no need to isolate the resulting intermediate beforehand, the2-(N,N-dialkylamine) acetyllactam obtained is reacted with an alkylatingagent such as methyl chloride or dimethyl sulfate at temperatures ofbetween 20 and 100° C., preferably between 70 and 80° C., to give thecorresponding 2-(N,N,N-trialkylammonium)acetyllactam salt.

The auxiliary base used is preferably the amines employed for thereaction.

The invention also provides bleaching detergents and cleaners (cleaningcompositions) which comprise the novel compounds as bleach activators.These detergents and cleaners commonly, in addition to a peroxy compoundand the cationic bleach activator, include surface-active compounds andother ingredients as well.

Suitable peroxy compounds are alkali metal peroxides, organic peroxidessuch as urea peroxide, and inorganic per salts, such as the perborates,percarbonates, perphosphates, persilicates and persulfates of alkalimetals. Mixtures of two or more of these compounds are likewisesuitable. Particular preference is given to sodium perboratetetrahydrate and, in particular, to sodium perborate monohydrate. Sodiumperborate monohydrate is preferred on account of its good stability onstorage and its ready solubility in water. Sodium percarbonate may bepreferred on environmental grounds.

Alkyl hydroperoxides constitute a further suitable group of peroxycompounds. Examples of these substances are cumene hydroperoxide andt-butyl hydroperoxide.

In detergents and cleaners of this kind the content by weight of thenovel cationic bleach activator can be from about 0.1% to 20%,preferably from 0.5% to 10%, in particular from 1% to 7.5%, togetherwith a peroxy compound. The proportion by weight of these peroxycompounds is commonly from 2% to 40%, preferably from 4% to 30%, inparticular from 10% to 25%.

The detergents and cleaners may also, in addition to the novel cationicbleach activators, include other suitable bleach activators, such asTAED, for example.

The surface-active substance can be derived from natural products, suchas soap, or can be a synthetic compound from the group consisting ofanionic, nonionic, amphoteric, zwitterionic and cationic surface-activesubstances or mixtures thereof. Numerous suitable substances arecommercially available and are described in the literature, for examplein "Surface active agents and detergents", Vol. 1 and 2, by Schwartz,Perry and Berch. The overall proportion of the surface-active compoundscan be up to 50% by weight, preferably from 1% by weight to 40% byweight, in particular from 4% by weight to 25% by weight.

Synthetic anionic surface-active substances are usually water-solublealkali metal salts of organic sulfates and sulfonates with alkylradicals of about 8 to 22 carbon atoms, the term "alkyl" including thealkyl substituents of higher aryl radicals.

Examples of suitable anionic detergents are sodium and ammonium alkylsulfates, especially the sulfates obtained by sulfation of higher (C₈ toC₁₈) alcohols; sodium and ammonium alkylbenzenesulfonates having analkyl radical of C₉ to C₂₀, especially linear secondary sodiumalkylbenzenesulfonates having an alkyl radical of C₁₀ to C₁₅ ; sodiumalkyl glycerol ether sulfates, especially the esters of the higheralcohols derived from tallow oil and coconut oil; the sodium sulfatesand sulfonates of the coconut fatty acid monoglycerides; sodium andammonium salts of the sulfuric acid esters of higher (C₉ to C₁₈)alkoxylated fatty alcohols, especially those alkoxylated with ethyleneoxide; the reaction products of the esterification of fatty acids withisethionic acid followed by neutralization with sodium hydroxide; sodiumand ammonium salts of the fatty acid amides of methyltaurine;alkanemonosulfonates, such as those from the reaction of α-olefins (C₈-C₂₀) with sodium bisulfite and those from the reaction of paraffinswith SO₂ and Cl₂₀ followed by basic hydrolysis, giving a mixture ofdifferent sulfonates; sodium and ammonium dialkyl sulfosuccinates withalkyl radicals of C₇ to C₁₂ ; and olefinsulfonates which are formed inthe reaction of olefins, especially C₁₀ to C₂ α-olefins, with SO₃followed by hydrolysis of the reaction products. The preferred anionicdetersives are sodium alkylbenzenesulfonates with alkyl radicals of C₁₅to C₁₈, and sodium alkyl ether sulfates with alkyl radicals of C₁₆ toC₁₈.

Examples of suitable nonionic surface-active compounds which are usedpreferably together with anionic surface-active compounds are, inparticular, the reaction products of alkylene oxides (commonly ethyleneoxide) with alkylphenols (alkyl radicals of C₅ to C₂₂), the reactionproducts generally containing from 5 to 25 ethylene oxide (EO) unitswithin the molecule; the reaction products of aliphatic (C₈ to C₁₈)primary or secondary, linear or branched alcohols with ethylene oxide,generally with from 6 to 30 EO, and the adducts of ethylene oxide withreaction products of propylene oxide and ethylenediamine. Other nonionicsurface-active compounds are alkylpolyglycosides, long-chain tertiaryamine oxides, long-chain tertiary phosphine oxides and dialkylsulfoxides.

Amphoteric or zwitterionic surface-active compounds can likewise be usedin the novel compositions, although this is usually not desirable owingto their high cost. If amphoteric or zwitterionic compounds are used,they are generally employed in small amounts in compositions whichpredominantly comprise anionic and nonionic surfactants.

Soaps as well can be used in the novel compositions, preferably in aproportion of less than 25% by weight. They are particularly suitable insmall amounts in binary (soap/anionic surfactant) or in ternary mixturestogether with nonionic or mixed synthetic anionic and nonionicsurfactants. The soaps used are preferably the sodium salts, and lesspreferably the potassium salts, of saturated or unsaturated C₁₀ to C₂₄fatty acids, or mixtures thereof. The proportions of such soaps can befrom 0.5% by weight to 25% by weight; smaller amounts of from 0.5% byweight to 5% by weight are generally sufficient for foam control.Proportions of soaps of between about 2% and about 20%, in particularbetween about 5% and about 10%, have a positive effect. This isespecially the case in hard water, where the soap acts as an additionalbuilder substance.

The detergents and cleaners generally also include a builder. Suitablebuilders are calcium-binding substances, precipitants, calcium-specificion exchangers and mixtures thereof. Examples of calcium-bindingsubstances include alkali metal polyphosphates, such as sodiumtripolyphosphate; nitrilotriacetic acid and its water-soluble salts; thealkali metal salts of carboxymethyloxysuccinic acid,ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid,benzenepolycarboxylic acids and citric acid; and polyacetylcarboxylates, as disclosed in U.S. Pat. No. 4,144,226 and U.S. Pat. No.4,146,495.

Examples of precipitants include sodium orthophosphate, sodium carbonateand soaps of long-chain fatty acids.

Examples of ion exchangers which are specific for calcium include thevarious types of water-insoluble, crystalline or amorphous aluminumsilicates, of which the zeolites are the best-known representatives.

These builder substances can be present in a proportion of from 5% byweight to 80% by weight, preferably from 10% by weight to 60% by weight.

In addition to the ingredients already mentioned, the detergents andcleaners may include any of the conventional additives in amounts whichare customary in such compositions. Examples of these additives includefoam formers, such as alkanolamides, especially the monoethanolamides ofpalm kernel oil fatty acids and coconut fatty acids; foam inhibitors,such as alkyl phosphates and alkylsilicones; graying inhibitors(antiredeposition agents) and similar auxiliaries, such as sodiumcarboxymethylcellulose and alkyl- or substituted alkylcellulose ethers;stabilizers, such as ethylenediaminetetraacetic acid; softeners fortextiles; inorganic salts, such as sodium sulfate; and, in usually smallamounts, fluorescent substances, fragrances, enzymes such as proteases,cellulases, lipases and amylases, disinfectants and colorants. Thebleach activators of this invention can be employed in a large number ofproducts. Such products include textile detergents, textile bleaches,surface cleaners, toilet cleaners, dishwasher detergents, and alsodenture cleansers. The detergents can be in solid or liquid form.

For reasons of stability and ease of handling it is advantageous to usethe bleach activators in the form of granules which in addition to thebleach activator include a binder. Various methods of preparing suchgranules are described in the patent literature, for example in CA-1 102966, GB-1 561 333, U.S. Pat. No. 4,087,369, EP-A-0 240 057, EP-A-0 241962, EP-A-0 101 634 and EP-A-0 062 523. Any of these methods can beemployed for the novel bleach activators.

The granules containing the bleach activators are generally added to thedetergent composition together with the other dry constituents, such asenzymes, inorganic peroxide bleaches, etc. The detergent composition towhich the activator granules are added can be obtained by variousmethods, such as dry mixing, extrusion or spray drying.

In a further embodiment the novel bleach activators are particularlysuitable for nonaqueous liquid detergents, together with a bleachingperoxy compound, for instance sodium perborate, in order to give thedetergent a high cleaning capacity for fabrics and textiles. Nonaqueousliquid detergents of this kind, which include pasty and gelatinousdetersive compositions, are known in the prior art and are described,for example, in U.S. Pat. No. 2,864,770, U.S. Pat. No. 2,940,938, U.S.Pat. No. 4,772,412, U.S. Pat. No. 3,368,977, GB-A-1205 711, GB-A-1 370377, GB-A-1 270 040, GB-A-1 292 352, GB-A-2 194 536, DE-A-2 233 771 andEP-A-0 028 849.

These compositions are in the form of a nonaqueous liquid medium inwhich a solid phase may be dispersed. The nonaqueous liquid medium canbe a liquid, surface-active substance, preferably a nonionicsurface-active substance; a nonpolar liquid medium, such as liquidparaffin; a polar solvent, for instance polyols, for example glycerol,sorbitol, ethylene glycol, alone or in conjunction with low molecularmass monofunctional alcohols such as ethanol or isopropanol; or mixturesthereof.

The solid phase may consist of builder substances, alkalis, abrasivesubstances, polymers, other solid ionic surface-active substances,bleaches, fluorescent substances, and other customary solid ingredients.

The following examples are intended to give an overview of theembodiments of the invention.

EXAMPLE 1

a) Synthesis of N-(chloroacetyl)pyrrolidone

To an initial charge of 81.0 g of 2-pyrrolidone in 200 ml of toluenethere are added, dropwise and with ice cooling, 54.7 g of chloroacetylchloride such that the temperature of the reaction mixture remains at 5°C. Following the addition the reaction mixture is stirred at roomtemperature for 6 hours. The resulting precipitate is filtered off withsuction and the solvent is removed in vacuo to give 74.5 g ofN-(chloroacetyl)pyrrolidone, corresponding to a yield of 97%.

b) Synthesis of 2-(N,N-diethylamine)acetylpyrrolidone

To 80.0 g of (chloroacetyl)pyrrolidone dissolved in 200 ml of toluenethere are added, dropwise and with ice cooling, 73.1 g of diethylamine,so that the temperature of the reaction mixture does not exceed 50° C.After the addition the reaction mixture is cooled to room temperatureand is stirred at this temperature for 2 hours more. The resultingprecipitate is filtered off with suction and the solvent is removed invacuo to give 74.9 g of 2-(N,N-diethylamine)acetylpyrrolidone,corresponding to a yield of 76%.

c) Synthesis of 2-(N,N-diethyl-N-methylammonium)acetylpyrrolidonetosylate (Compound No. 1)

To 19.8 g of 2-(N,N-diethylamine)acetylpyrrolidone in 30 ml ofacetonitrile there are added, dropwise, 73.1 g of methyl4-toluenesulfonate. After the addition the mixture is refluxed for 3hours and then the solvent is removed in vacuo to give a highly viscousoil which after recrystallization from isopropanol is obtained in theform of colorless crystals. The yield of2-(N,N-diethyl-N-methylammonium)acetylpyrrolidone tosylate is 33.5 g,corresponding to a yield of 87%.

Compounds 2 and 3 were prepared analogously (see page 13).

EXAMPLE 2

The combination of 200 ml of an aqueous solution of 5 g/l referencedetergent (WMP) obtained from WFK-Testgewebe GmbH, Krefeld, 150 mg ofsodium perborate monohydrate (PB*1) and 50 mg of an activator gave ableaching composition. Four pieces of fabric soiled with black tea (BC-1tea on cotton, 1.25 g, WFK) were added for a thirty-minute isothermalwashing experiment in a Linitest apparatus. After the predeterminedwashing time, the pieces of fabric were rinsed with water, dried andironed. The bleaching action was then determined by means of an ELREPHO2000 whiteness meter (Datacolor) by determining the differences inreflectance before and after bleaching.

Comparison experiments were carried out in which 50 mg of a novelactivator were added in addition to the detergent composition. Theinvestigations were repeated with different types of soiling (e.g. redwine, curry).

Bleach compositions with the bleach activators 1 to 3 were prepared.Their effectiveness was determined by comparing the reflectances of thefabric before and after the bleaching process. The results are indicatedin Table 1. The ΔΔR values indicate the improvement in the bleachingaction of the novel composition compared with PB*1:

    ΔΔ6R (QUAT-PB*1)=ΔR (QUAT)-ΔR (PB*1)

The compounds 1 to 3 are ##STR5##

                  TABLE 1    ______________________________________    Activator No.                 Δ R (QUAT)                           ΔΔ R (QUAT-PB*1)    ______________________________________    Tea, 40° C.    PB*1          7.8    1            10.7      2.9    2            12.3      4.5    3            10.1      2.3    Red Wine, 40° C.    PB*1         15.1    1            18.2      3.1    2            19.8      4.7    3            17.1      2.0    ______________________________________     The washing experiments show that the bleach compositions which include     novel bleach activators give better washing results than the comparison     detergent which lacks novel bleach activators.

We claim:
 1. A detergent or cleaner comprisinga) from 2 to 40% by weightof a peroxy compound; and b) from 0.1 to 20% by weight of a compound ofthe formula (I) ##STR6## as bleach activator wherein a) R₁, R₂ and R₃independently of one another are C₁ - to C₂₄ -alkyl, aryl, C₂ -C₂₄-alkenyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, or CH₂ --CO--L, or b) R₂ and R₃,together with the nitrogen atom to which they are attached, form aheterocyclic ring having from 4 to 6 carbon atoms, or form aheterocyclic ring having from 2 to 5 carbon atoms and 1 to 2 oxygenatoms, or a group ##STR7## L is a group of the formula ##STR8## n is anumber from 3 to 5, m is a number from 2 to 4, and X is an anion.
 2. Thedetergent or cleaner as claimed in claim 1, wherein the peroxy compoundis present in an amount of from 4 to 30% by weight.
 3. The detergent orcleaner as claimed in claim 2, wherein the peroxy compound is present inan amount of from 10 to 25% by weight.
 4. The detergent or cleaner asclaimed in claim 1, wherein the bleach activator is present in an amountof from 0.5 to 10% by weight.
 5. The detergent or cleaner as claimed inclaim 4, wherein the bleach activator is present in an amount of from 1to 7.5% by weight.
 6. The detergent or cleaner as claimed in claim 1,wherein the per compound is an inorganic material selected from thegroup consisting of perborate, percarbonate, perphosphate, persilicate,and monopersulfate.
 7. The detergent or cleaner as claimed in claim 1,wherein the per compound is an organic material selected from the groupconsisting of urea peroxide, cumene hydroperoxide and t-butylhydroperoxide.
 8. The detergent or cleaner as claimed in claim 1, whichfurther comprises from 1 to 80% of a detergent builder.
 9. The detergentor cleaner as claimed in claim 1, which further comprises an enzymeselected from the group consisting of proteases, cellulases, lipases,amylases and mixtures thereof in an amount which is effective forcleaning.
 10. The detergent or cleaner as claimed in claim 1, whichfurther comprises surface-active substances to be present in an amountof up to 50% by weight.
 11. The detergent or cleaner as claimed in claim1, which further comprises soaps to be present in an amount of up to 25%by weight.
 12. The detergent or cleaner as claimed in claim 8, whichcomprises the builder in an amount of from 5 to 80% by weight.